2-oxetanone derivative and process for production thereof

ABSTRACT

An aldehyde derivative represented by the general formula ( 2 ) is reacted with ketene in the presence of a Lewis acid catalyst to produce a novel  2 -oxetanone derivative ( 1 ), which is then purified to a  2 -oxetanone derivative having a high trans-isomer purity, and then converted to a vinyl derivative ( 3 ) through decarboxylation reaction.

TECHNICAL FIELD

The present invention relates to a novel 2-oxetanone derivativerepresented by the general formula (1) shown below. The 2-oxetanonederivative can be used as an intermediate for producing a vinylderivative represented by the general formula (3) shown below. Theinvention relates to a 2-oxetanone derivative, a method for producingthe 2-oxetanone derivative, and a method for producing a vinylderivative. The vinyl derivative according to the invention,particularly a trans-isomer thereof, has good electric and opticalcharacteristics and is useful as an intermediate material of a liquidcrystal for display and as a liquid crystal.

BACKGROUND ART

As an ordinary method for producing a trans-4-ethenylcyclohexanederivative, a method using a Wittig reaction of acyclohexanecarbaldehyde derivative and methyltriphenylphosphine halidehas been known (see, for example, Patent Document 1).

In this method, however, methyltriphenylphosphine halide as a rawmaterial is expensive, and it is necessary to remove completelytriphenylphosphine oxide by-produced for using the resultingtrans-4-ethenylcyclohexane derivative as a liquid crystal raw material,which requires a complicated purification process. Furthermore, adisposal cost is required for discarding the triphenylphosphine oxideby-produced, and thus the method involves problems in cost andenvironment.

As a method for producing the cyclohexanecarbaldehyde derivative used asa raw material of the reaction, a method of subjecting a cyclohexanonecompound represented by the general formula (6) to a Wittig reaction hasbeen known.

In the formula, R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxyhaving 1 to 15 carbons, halogenated alkyl having 1 to 15 carbons,halogenated alkoxy having 1 to 15 carbons, alkenyl having 2 to 10carbons, halogen or —C≡N; A₁, A₂ and A₃ are each independentlytrans-1,4-cyclohexylene in which arbitrary —CH₂— constituting the ringmay be replaced by —O— or —S—, 1,4-phenylene in which arbitrary hydrogenmay be replaced by fluorine, decahydronaphthalen-2,6-diyl,1,2,3,4-tetrahydronaphthalen-2,6-diyl or naphthalen-2,6-diyl; Z₁, Z₂ andZ₃ are each independently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or—OCH₂—; and j, k and l are each independently 0 or 1.

As a method for producing the cyclohexanecarbaldehyde derivative, amethod of oxidizing a carbinol compound represented by the generalformula (7) has been known.

In the formula, R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxyhaving 1 to 15 carbons, halogenated alkyl having 1 to 15 carbons,halogenated alkoxy having 1 to 15 carbons, alkenyl having 2 to 10carbons, halogen or —C≡N; A₁, A₂ and A₃ are each independentlytrans-1,4-cyclohexylene in which arbitrary —CH₂— constituting the ringmay be replaced by —O— or —S—, 1,4-phenylene in which arbitrary hydrogenmay be replaced by fluorine, decahydronaphthalen-2,6-diyl,1,2,3,4-tetrahydronaphthalen-2,6-diyl or naphthalen-2,6-diyl; Z₁, Z₂ andZ₃ are each independently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or—OCH₂—; and j, k and l are each independently 0 or 1.

However, a cyclohexanecarbaldehyde derivative obtained by these methodsis a mixture of a trans-isomer and a cis-isomer since the hydrogen atomat the α-position of the carbonyl group of the aldehyde is easilyepimerized (isomerized). A trans-4-ethenylcyclohexane derivative thathas a high trans-isomer purity is necessarily used as a raw material ofa liquid crystal for attaining good electric and opticalcharacteristics. Accordingly, it is necessary to remove the cis-isomerfrom the resulting cyclohexanecarbaldehyde derivative, but thecis-isomer cannot be easily removed, and purification withrecrystallization and column chromatography is necessarily performed(see, for example, Patent Document 2). Thus, the conventional methodsare never satisfactory.

[Patent Document 1] JP H9-52851 A/1997 (U.S. Pat. No. 5,709,820)

[Patent Document 2] JP H9-124521 A/1997

DISCLOSURE OF THE INVENTION

Accordingly, an object of the invention is to provide a novel oxetanonederivative and a method for producing the same, and to provide a methodfor producing efficiently a vinyl derivative, for example,trans-4-ethenylcyclohexane derivative as a typical example thereof, byusing the oxetanone derivative.

As a result of earnest investigations made by the inventors, a2-oxetanone derivative represented by the general formula (1) has beenfound as an intermediate of a vinyl derivative, and it has also beenfound that a vinyl derivative represented by the general formula (3) canbe produced efficiently by using the derivative, thereby the presentinvention has been completed.

Accordingly, the invention includes the followings.

[Item 1]

A 2-oxetanone derivative represented by the general formula (1):

wherein R₁ is hydrogen, alkyl having 1 to 20 carbons, halogen, —C≡N,—C≡C—C≡N, —N═C═O or —N═C═S, wherein arbitrary —CH₂— may be replaced by—O—, —S—, —CO— or —SiH₂—, arbitrary —(CH₂)₂— may be replaced by —CH═CH—or —C≡C—, and arbitrary hydrogen may be replaced by halogen in thealkyl; A₁, A₂, A₃ and A₄ are each independently 1,4-cyclohexylene,1,4-phenylene, decahydronaphthalen-2,6-diyl,1,2,3,4-tetrahydronaphthalen-2,6-diyl or naphthalen-2,6-diyl, whereinarbitrary —CH₂— may be replaced by —O—, —S—, —CO— or —SiH₂—, arbitrary—(CH₂)₂— may be replaced by —CH═CH— and arbitrary hydrogen may bereplaced by halogen in these rings, and arbitrary —CH═ may be replacedby —N═ in the 1,4-phenylene, provided that when A₁, A₂ and A₃ are each1,4-cyclohexylene, the steric configuration thereof is trans, and whenA₄ is 1,4-cyclohexylene, the steric configuration thereof may be trans,cis or a mixture of trans and cis; Z₁, Z₂, Z₃ and Z₄ are eachindependently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; j, kand l are each independently 0 or 1; m is 1; and n is an integer of from0 to 6.

[Item 2]

The 2-oxetanone derivative according to item 1 which is represented bythe general formula (1-1):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; Z₁, Z₂ and Z₃ are each independently a single bond,—CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; and j, k and l are eachindependently 0 or 1.

[Item 3]

A 2-oxetanone derivative represented by the general formula (1-2):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 4]

A 2-oxetanone derivative represented by the general formula (1-3):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 5]

A 2-oxetanone derivative represented by the general formula (I-4):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 6]

A 2-oxetanone derivative represented by the general formula (1-5):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 7]

A 2-oxetanone derivative represented by the general formula (1-6):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 8]

A 2-oxetanone derivative represented by the general formula (1-7):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 9]

A 2-oxetanone derivative represented by the general formula (1-8):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 10]

The 2-oxetanone derivative according to item 1 which is represented bythe general formula (1-9):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; Z₁, Z₂ and Z₃ are each independently a single bond,—CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; and j, k and l are eachindependently 0 or 1.

[Item 11]

A 2-oxetanone derivative represented by the general formula (1-10):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.

[Item 12]

4-(4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone,4-(4-(trans-4-butylcyclohexyl)cyclohexyl)-2-oxetanone or4-(4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone.

[Item 13]

A method for producing a 2-oxetanone derivative represented by thegeneral formula (1), comprising reacting an aldehyde derivativerepresented by the general formula (2) with ketene in the presence of aLewis acid catalyst:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂, A₃ and A₄ are each independently 1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl, provided that when A₁, A₂ and A₃ are each1,4-cyclohexylene, the steric configuration thereof is trans, and whenA₄ is 1,4-cyclohexylene, the steric configuration thereof may be trans,cis or a mixture of trans and cis; Z₁, Z₂, Z₃ and Z₄ are eachindependently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; j, kand l are each independently 0 or 1; m is 1; and n is an integer of from0 to 6,

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (2).

[Item 14]

A method for producing a vinyl derivative represented by the generalformula (3), comprising subjecting a 2-oxetanone derivative representedby the general formula (1) to decarboxylation under heating:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂, A₃ and A₄ are each independently 1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl, provided that when A₁, A₂ and A₃ are each1,4-cyclohexylene, the steric configuration thereof is trans, and whenA₄ is 1,4-cyclohexylene, the steric configuration thereof may be trans,cis or a mixture of trans and cis; Z₁, Z₂, Z₃ and Z₄ are eachindependently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; j, kand l are each independently 0 or 1; m is 1; and n is an integer of from0 to 6,

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (1).

[Item 15]

A method for producing a vinyl derivative represented by the generalformula (3), comprising reacting an aldehyde derivative represented bythe general formula (2) with ketene in the presence of a Lewis acidcatalyst to produce a 2-oxetanone derivative represented by the generalformula (1); purifying the compound represented by the general formula(1) wherein A₄ is trans-1,4-cyclohexylene in which arbitrary —CH₂—constituting the ring may be replaced by —O— or —S—, throughrecrystallization; and subjecting the compound to decarboxylation underheating:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; A₄ is 1,4-cyclohexylene in which arbitrary —CH₂—constituting the ring may be replaced by —O— or —S—; Z₁, Z₂, Z₃ and Z₄are each independently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or—OCH₂—; j, k and l are each independently 0 or 1; m is 1; and n is aninteger of from 0 to 6,

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (2),

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (2), provided that A₄ istrans-1,4-cyclohexylene in which arbitrary —CH₂— constituting the ringmay be replaced by —O— or —S—.

[Item 16]

A method for producing a vinyl derivative represented by the generalformula (3-1) wherein 1,4-cyclohexylene bonded to aldehyde has atrans-isomer, comprising reacting an aldehyde derivative represented bythe general formula (2-1) with ketene in the presence of a Lewis acidcatalyst to produce a 2-oxetanone derivative represented by the generalformula (1-1); purifying the compound represented by the general formula(1-1) wherein 1,4-cyclohexylene bonded to aldehyde has a trans-isomerthrough recrystallization; and subjecting the compound todecarboxylation under heating:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; Z₁, Z₂ and Z₃ are each independently a single bond,—CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; and j, k and l are eachindependently 0 or 1,

wherein R₁, A₁, A₂, A₃, Z₁, Z₂, Z₃, j, k and l have the same meanings asin the formula (2-1),

wherein R₁, A₁, A₂, A₃, Z₁, Z₂, Z₃, j, k and l have the same meanings asin the formula (2-1).

According to the invention, a novel 2-oxetanone derivative as asynthesis intermediate of a liquid crystal material can be provided froman aldehyde derivative. A vinyl derivative having a high purity andcontaining no triphenylphosphine oxide can be synthesized throughdecarboxylation reaction of the 2-oxetanone derivative. From the2-oxetanone derivative of the invention, the cis-isomer can be easilyremoved through recrystallization to provide a 2-oxetanone derivativehaving high trans-isomer purity.

BEST MODE FOR CARRYING OUT THE INVENTION

The 2-oxetanone derivative of the invention is represented by formula(1):

In the formula, R₁ is hydrogen, alkyl having 1 to 20 carbons, halogen,—C≡N, —C≡C—C≡N, —N═C═O or —N═C═S, wherein arbitrary —CH₂— may bereplaced by —O—, —S—, —CO— or —SiH₂—, arbitrary —(CH₂)₂— may be replacedby —CH═CH— or —C≡C—, and arbitrary hydrogen may be replaced by halogenin the alkyl; A₁, A₂, A₃ and A₄ are each independently1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalen-2,6-diyl,1,2,3,4-tetrahydronaphthalen-2,6-diyl or naphthalen-2,6-diyl, whereinarbitrary —CH₂— may be replaced by —O—, —S—, —CO— or —SiH₂—, arbitrary—(CH₂)₂— may be replaced by —CH═CH— and arbitrary hydrogen may bereplaced by halogen in these rings, and arbitrary —CH═ may be replacedby —N═ in the 1,4-phenylene, provided that when A₁, A₂ and A₃ are each1,4-cyclohexylene, the steric configuration thereof is trans, and whenA₄ is 1,4-cyclohexylene, the steric configuration thereof may be trans,cis or a mixture of trans and cis; Z₁, Z₂, Z₃ and Z₄ are eachindependently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; j, kand l are each independently 0 or 1; m is 1; and n is an integer of from0 to 6.

The 2-oxetanone derivative represented by the general formula (1)includes the following compounds, but is not limited to the followingcompounds.

In the formulas (1-1) to (1-10), R₁ is hydrogen, alkyl having 1 to 15carbons, alkoxy having 1 to 15 carbons, halogenated alkyl having 1 to 15carbons, halogenated alkoxy having 1 to 15 carbons, alkenyl having 2 to10 carbons, halogen or —C≡N.

In the formulas (1-1) to (1-9), A₁, A₂ and A₃ are each independentlytrans-1,4-cyclohexylene in which arbitrary —CH₂— constituting the ringmay be replaced by —O— or —S—, 1,4-phenylene in which arbitrary hydrogenmay be replaced by fluorine, decahydronaphthalen-2,6-diyl,1,2,3,4-tetrahydronaphthalen-2,6-diyl or naphthalen-2,6-diyl; Z₁, Z₂ andZ₃ are each independently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or—OCH₂—; and j, k and l are each independently 0 or 1.

Examples of (1-2) include4-(4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone,4-(4-(trans-4-butylcyclohexyl)cyclohexyl)-2-oxetanone,4-(4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone and the like.

Examples of (1-7) include4-(4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)-2-oxetanone and thelike.

The method for producing the oxetanone derivative will be described.

The 2-oxetanone derivative (1) can be produced by introducing ketene toan organic solvent solution of an aldehyde derivative (2) and acatalytic amount of a Lewis acid. An aldehyde derivative to be usedherein is represented by the general formula (2):

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (1). The compound represented by thegeneral formula (2) can be synthesized by a method that has beenreported. The compound represented by the general formula (2) can besynthesized by a method that is disclosed in the known literatures.Representative examples of the literatures for synthesis are shownbelow. 4-(trans-4-Propylcyclohexyl)cyclohexylcarbaldehyde: JP H9-124521A/1997 and Liquid Crystal, 10, 261 (1991),4-(trans-4-pentylcyclohexyl)cyclohexylcarbaldehyde: U.S. Pat. No.4,323,473, 4-(4-cycnophenyl)cyclohexylcarbaldehyde,4-(trans-4-(3,4-difluorophenyl)cyclohexyl)cyclohexyl-carbaldehyde: U.S.Pat. No. 5,185,098,4-(trans-4-(3,4,5-trifluorophenyl)cyclohexyl)cyclohexyl-carbaldehyde: JPH6-211711 A/1994,4-(trans-4-(3-fluoro-4-methylphenyl)cyclohexyl)cyclohexyl-carbaldehyde:Liquid Crystal, 16, 491 (1994),4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl-carbaldehyde: LiquidCrystal, 16, 491 (1991), 3-(trans-4-(4-cyanophenyl)cyclohexyl)propanal:JP H1-216967 A/1989,3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propanal: JP H1-175947A/1989, [1,1′:4′,1″-terphenyl]-4-propanal: Journal of American ChemicalSociety, 126, 2807 (2004)

The ketene to be used for reaction with the aldehyde derivativerepresented by the general formula (2) may be one obtained by anordinary production method, and for example, ketene obtained by thermaldecomposition of acetone, thermal decomposition of acetic acid, and thelike may be used.

As the Lewis acid, various kinds of Lewis acids may be used, such asaluminum chloride, aluminum bromide, zinc chloride, iron chloride, zincbromide, titanium chloride, boron chloride, boron bromide and the like,and in particular, iron chloride and a boron trifluoride ether complexare preferred from the standpoint of activity. The catalyst is generallyused in a range of from 0.01 to 20% by mol, and preferably in a range offrom 0.1 to 10% by mol, based on the aldehyde derivative (3).

As the organic solvent, a solvent capable of dissolving the aldehydederivative may be used. Examples thereof include a haloalkane, such asdichloromethane, chloroform and the like, an ester, such as ethylacetate and the like, an alkylbenzene, such as toluene and the like, anether solvent, such as diethyl ether, tetrahydrofuran and the like, andmixed solvents thereof. The using amount of the organic solvent is notparticularly limited, and the organic solvent is generally used in arange of about from 0.5 to 30 times the aldehyde derivative (2) byweight.

The reaction with ketene is performed in the solvent, and the order ofcharging the ketene and the aldehyde derivative (2) is not particularlylimited, and whichever may be charged firstly. The reaction temperaturemay be in a range of from −78 to 100° C., and preferably in a range offrom −40 to 30° C.

The resulting 2-oxetanone derivative may be purified by such a method asrecrystallization or the like.

The recrystallization may be performed on standing still or on stirring.Crystals thus deposited may be separated by a known method, such asfiltration, suction filtration, centrifugal separation and the like. Inthe case where the crystals deposited contain the cis-isomer (i.e., thecompound represented by the general formula (1) where the stericconfiguration of A₄ is cis), the resulting crystals may be furtherrecrystallized to lower the content of the cis-isomer. The mother liquidrecovered may be again subjected to recrystallization to recover thetrans-isomer (i.e., the compound represented by the general formula (1)where the steric configuration of A₄ is trans) with high purity.Repetitive operation of recrystallization enables effective recovery andpurification of the trans-isomer from the mother liquid.

Specifically, the 2-oxetanone derivative represented by the generalformula (1) is dissolved in a suitable organic solvent to prepare asaturated solution. The saturated solution can be formed by dissolvingthe 2-oxetanone derivative represented by the general formula (1) underheating, or by concentrating the solution. Preferred examples of thesolvent include a hydrocarbon solvent, such as hexane, heptane,cyclohexane, toluene and the like, an ether solvent, such as diethylether, dibutyl ether and the like, an ester solvent, such as methylacetate, ethyl acetate, propyl acetate and the like, an alcohol solvent,such as methanol, ethanol, isopropanol and the like, and mixed solventsthereof.

The concentration of the 2-oxetanone derivative in the saturatedsolution varies depending on the solvent used and the crystallizationtemperature, and in general, is preferably in a range of from 3 to 40%by weight.

The vinyl derivative represented by the general formula (3) can beproduced by subjecting the 2-oxetanone derivative (trans-isomer)represented by the general formula (1) to decarboxylation. Thedecarboxylation reaction in the present invention is generally performedin a range of from 100 to 250° C., and preferably in a range of from 150to 200° C. The temperature is preferably 100° C. or more for providing asufficient reaction rate, and is preferably 250° C. or less forpreventing polymerization, decomposition and isomerization of the vinylgroup from occurring.

A solvent and a catalyst are not always necessary, but may be used forcontrolling the reaction temperature. Examples of the solvent to be usedinclude an ester solvent, such as hexyl acetate, octyl acetate, butylacetate and the like, a non-protonic polar solvent, such asdimethylsulfoxide, dimethylamide and the like, and the like. The usingamount of the organic solvent is not particularly limited, and isgenerally from 0.5 to 30 times the 2-oxetanone derivative by weight.

It is sometimes preferable that an antioxidant is added before startingthe decarboxylation reaction for enhancing the storage stability of thecoarse liquid of the vinyl derivative obtained through thedecarboxylation reaction. Examples of the antioxidant include BTH. Theaddition amount of the antioxidant is from 1 to 10,000 ppm, andparticularly preferably from 10 to 500 ppm, based on the 2-oxetanonederivative.

The trans-isomer of the 2-oxetanone derivative with high purity isobtained through recrystallization in the aforementioned manners, andthen the trans-isomer of the vinyl derivative (i.e., the compoundrepresented by the general formula (3) where the steric configuration ofA₄ is trans) with high purity can be produced by subjecting the2-oxetanone derivative to decarboxylation. The trans-isomer of the vinylderivative is particularly useful as a material for liquid crystal andthe like.

EXAMPLES

¹H-NMR: A proton nuclear magnetic resonance spectrum was measured withGSX400 (400 MHz) of JEOL Ltd. with tetramethylsilane as an internalstandard. Analysis of cis- and trans-isomers of the 4-substitutedcyclohexyl-2-oxetanone derivative was calculated from the methine protonratio of the β-lactone ring in ¹H-NMR. The advantages of the presentinvention will be described with reference to examples below, but thepresent invention is not limited thereto.

Example 1 Synthesis of4-(4-(trans-4-propylcyclohexyl)-cyclohexyl)-2-oxetanone

4-(trans-4-Propylcyclohexyl)cyclohexylcarbaldehyde (1 g, 3.8 mmol, ratiooftrans-4-(trans-4-propylcyclohexane)-cyclohexanecarbaldehyde/cis-4-(trans-4-propylcyclohexyl)-cyclohexanecarbaldehyde=99.7/0.3)was dissolved in ethyl acetate (9 g), and iron chloride (FeCl₃, 10 mg,0.06 mmol) was added thereto. 1.3 equivalents of ketene was introducedinto the solution at 30° C. over 60 minutes. After completing theintroduction of ketene, nitrogen was introduced for 30 minutes toeliminate the unreacted ketene, and the reaction was terminated byadding an aqueous solution having dissolved therein NaHCO₃ (31 mg, 0.37mmol) corresponding to 6 equivalents of the catalyst. The resultingsolution was concentrated to provide4-(4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone (ratio of4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone/4-(cis-4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone=99.7/0.3)(0.90 g, 2.8 mmol, yield: 74%)).

The ¹H-NMR spectrum was substantially the same as4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone shown inExample 2, but the methine group of 2-oxetanone having cyclohexylsubstituted thereon derived from4-(cis-4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone was observedin the following region.

¹H-NMR (CDCl₃) δ: 4.46-4.51 (m, cyclohexyl-CH)

Example 2 Purification of4-(trans-4-(trans-4-propyl-cyclohexyl)cyclohexyl)-2-oxetanone

The mixture of4-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)-2-oxetanone/4-(cis-4-(trans-4-propyl-cyclohexyl)cyclohexyl)-2-oxetanone=99.7/0.3synthesized in Example 1 was coarsely purified with silica gelchromatography, and then dissolved in ethyl acetate (4 mL) at 30° C.,followed by cooling to 5° C. Crystals deposited after lapsing 5 minuteswere suction-filtered and dried under reduced pressure to provide4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone/4-(cis-4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone=100/0(0.90 g, 2.8 mmol, yield: 74%).

¹H-NMR (CDCl₃) δ: 0.82-1.81 (m, 26H, CH₃, CH₃—CH₂—CH₂, CH₂—CH₂—CH,(CH₂)₃—CH, CH—CH₂—CH₂×8, CH—CH—(CH₂)₂×2), 1.99-2.01 (m, 1H,—CH-4-oxetanone), 3.11, 3.42 (dd, 2H, J=16.14.4 Hz, J=16.1 5.9 Hz,CH—CH₂—CO), 4.15-4.20 (m, 1H, cyclohexyl-CH)

Example 3 Synthesis oftrans-1-ethenyl-4-(trans-4-propyl-cyclohexyl)cyclohexane

4-(trans-4-(trans-4-Propylcyclohexyl)cyclohexyl)-2-oxetanone (1 g, 3.1mmol) obtained in Example 2 was placed in a reactor, the interior ofwhich was then sufficiently replaced by nitrogen. The reactor washeated, and after heating to 170° C. for 3 hours, it was cooled to roomtemperature. The resulting solid was dissolved in heptane and purifiedwith silica gel chromatography to providetrans-1-ethenyl-4-(trans-4-propyl-cyclohexyl)cyclohexane (0.83 g, 30mmol, yield: 95%).

Example 4 Synthesis of4-(4-(trans-4-pentylcyclohexyl)-cyclohexyl)-2-oxetanone

In the same manner as in Example 1,4-(4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone (ratio of4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone/4-(cis-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone=98/2(yield: 70%)) was obtained by using4-(trans-4-pentylcyclohexyl)cyclohexylcarbaldehyde (1 g, 3.8 mmol, ratiooftrans-4-(trans-4-pentylcyclohexyl)cyclohexyl-carbaldehyde/cis-4-(trans-4-pentylcyclohexyl)cyclohexyl-carbaldehyde=98/2).

The ¹H-NMR spectrum was substantially the same as4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone shown inExample 5, but the methine group of 2-oxetanone having cyclohexylsubstituted thereon derived from4-(cis-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone was observedin the following region.

¹H-NMR (CDCl₃) δ: 4.46-4.51 (m, cyclohexyl-CH)

Example 5 Purification of4-(trans-4-(trans-4-pentyl-cyclohexyl)cyclohexyl)-2-oxetanone

Ethyl acetate (40 mL) was added to the mixture of4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone and4-(cis-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone (mixingratio: 98/2, 10.8 g, 28.1 mmol) synthesized in Example 4 and coarselypurified with silica gel chromatography, to dissolve the mixture at 30°C., followed by cooling to −20° C. Crystals deposited after lapsing 5minutes were suction-filtered and dried under reduced pressure toprovide4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone/4-(cis-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone=99.9/0.1(8.3 g, 25.8 mmol, yield: 92%). Ethyl acetate (30 mL) was added to theresulting crystals, and the same operation was performed to provide4-(trans-4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone(trans-isomer: 100%, 7.3 g, 24.2 mmol, yield: 94%).

¹H-NMR (CDCl₃) δ: 0.82-1.81 (m, 30H, CH₃, CH₃—CH₂—CH₂, CH₂—CH₂—CH₂×2,CH₂—CH₂—CH, (CH₂)₃—CH, CH—CH₂—CH₂×8, CH—CH—(CH₂)₂×2), 1.99-2.01 (m, 1H,(CH₂)CH-4-oxetanone), 3.11, 3.42 (dd, 2H, J=16.14.4 Hz, J=16.15.9 Hz,CH—CH₂—CO), 4.15-4.20 (m, 1H, cyclohexyl-CH)

Example 6 Synthesis oftrans-1-ethenyl-4-(trans-4-pentyl-cyclohexyl)cyclohexane

1-Pentyl-trans-4-(trans-4-cyclohexyl)cyclohexyl-2-oxetanone obtained inExample 5 was placed in a reactor, the interior of which was thensufficiently replaced by nitrogen. The reactor was heated, and afterheating to 170° C. for 3 hours, it was cooled to room temperature. Theresulting solid was dissolved in heptane and purified with silica gelchromatography to providetrans-1-ethenyl-4-(trans-4-pentylcyclohexyl)-cyclohexane at a yield of95%.

Example 7 Synthesis of4-(4-(trans-4-(4-methylphenyl)-cyclohexyl)cyclohexyl)-2-oxetanone

4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexane-carbaldehyde (20.6 g,72 mmol, ratio oftrans-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexanecarbaldehyde/cis-4-(trans-4-(4-methylphenyl)cyclohexyl)-cyclohexylcarbaldehyde=98/2) wasdissolved in ethyl acetate (380 g), and iron chloride (FeCl₃, 0.2 g, 1.2mmol) was added thereto. 3.7 equivalents of ketene was introduced intothe solution at 40° C. over 150 minutes. After completing theintroduction of ketene, nitrogen was introduced for 30 minutes toeliminate the unreacted ketene. The resulting solution was concentratedto provide4-(4-(trans-4-(4-methylphenyl)-cyclohexyl)cyclohexyl)-2-oxetanone (ratioof 4-(trans-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)-2-oxetanone/4-(cis-4-(trans-4-(4-methylphenyl)cyclohexyl)-cyclohexyl)-2-oxetanone=98/2)(27.8 g, 64 mmol, yield: 88%)).

The ¹H-NMR spectrum was substantially the same as4-(trans-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)-2-oxetanoneshown in Example 8, but the methine group of 2-oxetanone havingcyclohexyl substituted thereon derived from4-(cis-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)-2-oxetanone wasobserved in the following region.

¹H-NMR (CDCl₃) δ: 4.48-4.51 (m, cyclohexyl-CH—O)

Example 8 Purification of4-(trans-4-(trans-4-(4-methyl-phenyl)cyclohexyl)cyclohexyl)-2-oxetanone

The mixture of4-(trans-4-(trans-4-(4-methylphenyl)-cyclohexyl)cyclohexyl)-2-oxetanoneand4-(cis-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)-2-oxetanone=98/2synthesized in Example 7 was coarsely purified with silica gelchromatography, and then dissolved in toluene (80 mL) at 60° C., andthen heptane (20 mL) was added thereto, followed by cooling to −40° C.Crystals deposited after lapsing 5 minutes were suction-filtered anddried under reduced pressure to provide4-(trans-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)-2-oxetanone/4-(cis-4-(trans-4-(4-methylphenyl)cyclohexyl)-cyclohexyl)-2-oxetanone=99.8/0.2(17.0 g, 52 mmol, yield: 94%). The resulting crystals were subjected tothe same operation by using toluene (68 mL) and heptane (17 mL) toprovide4-(trans-4-(trans-4-(4-methylphenyl)cyclohexyl)cyclohexyl)-2-oxetanone(trans-isomer: 100%, 16.2 g, 50 mmol, yield: 97%).

¹H-NMR (CDCl₃) δ: 1.04-1.92 (m, 18H, CH—CH ₂—CH₂×8, CH—CH—(CH₂)₂×2),2.02-2.05 (m, 1H, —CH-4-oxetanone), 2.31 (s, 3H, Ph-CH ₃), 2.38-2.45 (m,1H, Ph-CH—(CH₂)₂, 3.10, 3.42 (dd, 2H, J=16.1 Hz 4.4 Hz, J=16.55.9 Hz,CH—CH ₂—CO), 4.17-4.19 (m, 1H, cyclohexyl-CH—O), 7.10 (s, 4H, Ph-H)

Example 9 Synthesis oftrans-1-ethenyl-4-(trans-4-(4-methyl-phenyl)cyclohexyl)cyclohexane

4-(trans-4-(trans-4-(4-Methylphenyl)cyclohexyl)-cyclohexyl)-2-oxetanone(3 g, 9.2 mmol) obtained in Example 8 was placed in a reactor, theinterior of which was then sufficiently replaced by nitrogen. Thereactor was heated, and after heating to 170° C. for 3 hours, it wascooled to room temperature. The resulting solid was dissolved in heptaneand purified with silica gel chromatography to providetrans-1-ethenyl-4-(trans-4-(4-methylphenyl)cyclohexyl)-cyclohexane (2.4g, 8.5 mmol, yield: 89%).

The 2-oxetanone derivatives (compound (1) to compound (98)) shown belowcan be easily produced according to the method disclosed in Examples.

No.

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

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79

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81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

98

1. A 2-oxetanone derivative represented by the general formula (1):

wherein R₁ is hydrogen, alkyl having 1 to 20 carbons, halogen, —C≡N,—C≡C—C≡N, —N═C═O or —N═C═S, wherein arbitrary —CH₂— may be replaced by—O—, —S—, —CO— or —SiH₂—, arbitrary —(CH₂)₂— may be replaced by —CH═CH—or —C≡C—, and arbitrary hydrogen may be replaced by halogen in thealkyl; A₁, A₂, A₃ and A₄ are each independently 1,4-cyclohexylene,1,4-phenylene, decahydronaphthalen-2,6-diyl,1,2,3,4-tetrahydronaphthalen-2,6-diyl or naphthalen-2,6-diyl, whereinarbitrary —CH₂— may be replaced by —O—, —S—, —CO— or —SiH₂—, arbitrary—(CH₂)₂— may be replaced by —CH═CH—, and arbitrary hydrogen may bereplaced by halogen in these rings, and arbitrary —CH═ may be replacedby —N═ in the 1,4-phenylene, provided that when A₁, A₂ and A₃ are each1,4-cyclohexylene, the steric configuration thereof is trans, and whenA₄ is 1,4-cyclohexylene, the steric configuration thereof may be trans,cis or a mixture of trans and cis; Z₁, Z₂, Z₃ and Z₄ are eachindependently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; j, kand l are each independently 0 or 1; m is 1; and n is an integer of from0 to
 6. 2. The 2-oxetanone derivative according to claim 1 which isrepresented by the general formula (1-1):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; Z₁, Z₂ and Z₃ are each independently a single bond,—CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; and j, k and l are eachindependently 0 or
 1. 3. A 2-oxetanone derivative represented by thegeneral formula (1-2):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.4. A 2-oxetanone derivative represented by the general formula (1-3):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.5. A 2-oxetanone derivative represented by the general formula (1-4):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.6. A 2-oxetanone derivative represented by the general formula (1-5):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.7. A 2-oxetanone derivative represented by the general formula (1-6):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.8. A 2-oxetanone derivative represented by the general formula (1-7):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.9. A 2-oxetanone derivative represented by the general formula (1-8):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.10. The 2-oxetanone derivative according to claim 1 which is representedby the general formula (1-9):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; Z₁, Z₂ and Z₃ are each independently a single bond,—CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; and j, k and l are eachindependently 0 or
 1. 11. A 2-oxetanone derivative represented by thegeneral formula (1-10):

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N.12. 4-(4-(trans-4-propylcyclohexyl)cyclohexyl)-2-oxetanone,4-(4-(trans-4-butylcyclohexyl)cyclohexyl)-2-oxetanone or4-(4-(trans-4-pentylcyclohexyl)cyclohexyl)-2-oxetanone.
 13. A method forproducing a 2-oxetanone derivative represented by the general formula(1), comprising reacting an aldehyde derivative represented by thegeneral formula (2) with ketene in the presence of a Lewis acidcatalyst:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂, A₃ and A₄ are each independently 1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl, provided that when A₁, A₂ and A₃ are each1,4-cyclohexylene, the steric configuration thereof is trans, and whenA₄ is 1,4-cyclohexylene, the steric configuration thereof may be trans,cis or a mixture of trans and cis; Z₁, Z₂, Z₃ and Z₄ are eachindependently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; j, kand l are each independently 0 or 1; m is 1; and n is an integer of from0 to 6,

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (2).
 14. A method for producing a vinylderivative represented by the general formula (3), comprising subjectinga 2-oxetanone derivative represented by the general formula (1) todecarboxylation under heating:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂, A₃ and A₄ are each independently 1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl, provided that when A₁, A₂ and A₃ are each1,4-cyclohexylene, the steric configuration thereof is trans, and whenA₄ is 1,4-cyclohexylene, the steric configuration thereof may be trans,cis or a mixture of trans and cis; Z₁, Z₂, Z₃ and Z₄ are eachindependently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; j, kand l are each independently 0 or 1; m is 1; and n is an integer of from0 to 6,

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (1).
 15. A method for producing a vinylderivative represented by the general formula (3), comprising reactingan aldehyde derivative represented by the general formula (2) withketene in the presence of a Lewis acid catalyst to produce a 2-oxetanonederivative represented by the general formula (1); purifying thecompound represented by the general formula (1), wherein A₄ istrans-1,4-cyclohexylene in which arbitrary —CH₂— constituting the ringmay be replaced by —O— or —S—, through recrystallization; and subjectingthe compound to decarboxylation under heating:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; A₄ is 1,4-cyclohexylene in which arbitrary —CH₂—constituting the ring may be replaced by —O— or —S—; Z₁, Z₂, Z₃ and Z₄are each independently a single bond, —CH₂CH₂—, —(CH₂)₄—, —CH₂O— or—OCH₂—; j, k and l are each independently 0 or 1; m is 1; and n is aninteger of from 0 to 6,

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (2),

wherein R₁, A₁, A₂, A₃, A₄, Z₁, Z₂, Z₃, Z₄, j, k, l, m and n have thesame meanings as in the formula (2), provided that A₄ istrans-1,4-cyclohexylene in which arbitrary —CH₂— constituting the ringmay be replaced by —O— or —S—.
 16. A method for producing a vinylderivative represented by the general formula (3-1), wherein1,4-cyclohexylene bonded to aldehyde has a trans-isomer, comprisingreacting an aldehyde derivative represented by the general formula (2-1)with ketene in the presence of a Lewis acid catalyst to produce a2-oxetanone derivative represented by the general formula (1-1);purifying the compound represented by the general formula (1-1), wherein1,4-cyclohexylene bonded to aldehyde has a trans-isomer, throughrecrystallization; and subjecting the compound to decarboxylation underheating:

wherein R₁ is hydrogen, alkyl having 1 to 15 carbons, alkoxy having 1 to15 carbons, halogenated alkyl having 1 to 15 carbons, halogenated alkoxyhaving 1 to 15 carbons, alkenyl having 2 to 10 carbons, halogen or —C≡N;A₁, A₂ and A₃ are each independently trans-1,4-cyclohexylene in whicharbitrary —CH₂— constituting the ring may be replaced by —O— or —S—,1,4-phenylene in which arbitrary hydrogen may be replaced by fluorine,decahydronaphthalen-2,6-diyl, 1,2,3,4-tetrahydronaphthalen-2,6-diyl ornaphthalen-2,6-diyl; Z₁, Z₂ and Z₃ are each independently a single bond,—CH₂CH₂—, —(CH₂)₄—, —CH₂O— or —OCH₂—; and j, k and l are eachindependently 0 or 1,

wherein R₁, A₁, A₂, A₃, Z₁, Z₂, Z₃, j, k and l have the same meanings asin the formula (2-1),

wherein R₁, A₁, A₂, A₃, Z₁, Z₂, Z₃, j, k and l have the same meanings asin the formula (2-1).